Rust inhibiting composition



Q... null Patented Dec. 1, 1953 UNITED TATIETS PATENT orator:

. RUST ,INHIBLTING .CQMROSITION Knapel F. Schiermeier and Herbert A.Poitz,

AltonfIlL, assignors to Shellflevelopment Goml Fpany, :San :Franciscc,Galifi, ta corporation of Delaware 'N Draw ns- Ap c nTAPriPZSLlMB,

"Serial No.23;398

fiadiaims- This invention relates to an all purpose cor---rosion-inhibiting composition. 'Moreparticularly,

this invention "pertains to corrosion inhibiting compositions having the=ability of displacing moisture, corrosive materials and the like from"metal surfaces and forming thereon 'a tena-cious protective film, whichis impervious to moisture andpthercontaminants.

Itis vvell known that moisture, corrosive fluids and "gases, e. g. -H2S,S02, 'etc. readily attack not only metallic -surfaces=but non-metallicsurfaces and :cause corrosion, rusting, ;pitting and other damagestosuch surfaces. Also-aqueous solutions when in contact "with a metallicsurface readily attack it and cause corrosionand rusting.

Under certainconditionsthe problem of corrosion becomes exceedinglyseriousbecauseoncestarted it ibecomes progressively "accelerated. "Ihus,oils containing small amounts :of water, *become "verycorro'sivettozcontactingmetals. 'This-is'dueto the Tact that oils andparticularly liquid petroleum hydrocarbons are relatively good-solubilizers 'of oxygen and anymoisture'presenttherein'becomessurrounded .by an almost inexhaustible store;of oxygen. 'Moisture.;under such conditions is -inhibitejd from evaporating andsince:the:rate of transfer of oxy en "from hydrocarbons,-such as mineraloil orgasoline, to water'is"limited,'ideal conditions 'for rusting andcorrosion ,are .;set up. The presence of, electrolytes and formation ofcorrosive decomposition products'in oils and'theplike alsogreatly'increase the rate of corrosivity,

Under conditions wherefin addition to those enumerated, elevated,temperature is encountered,

corrosion activity is reatly ac eleratedmoisture, salt sp ays an'dpthercontamina ts m i i compo on products andccrrosWe gases formed duringoperation of Busin ss-such aslinternal combustionengines, diesel.engines,;aircraft engines, turbines .and various .other machinery and-imiustrial eq pment, read ly attac and rust .or ..co.r rocle contactingmetal surfaces. .The damage thus ,causeid. is not .,-to Ithe .metal--sura,ce

alone for rust; particles frequently break ,ofiand enter the circulatingsystemof enginesand cause plugging, clogging, and fouling of conduitlines, columns, plates, and the lines .of cracking equip--ment,-tubes,'evaporatorsetc.

"Corrosionof alloyed bearings and other alloyed suflaces due to contact'with "Water "can attain such an aggravated-stage as to-causegreatiatigue stresses tobe set up, which ultimately results i intracking of the metal.

The :problem is equally serious "when "com- =ba-ting rusting andcorrosion ofsteel *druma'stor- :age-tanksnsedto store gasoline'hydrocarbon-oils anditnetlike. Moistune :adhering to :pickled steel,

quenched steel, :equipment such as instruments, engine-starters andgeneratorsron landingmrafts,

vhydraulic systems, machinery for metal ,proeessingl-and the like arealso extremel-y susceptiple'rto corrosion and must be protected.T1'leq1ll'flb16lllrl5 particularly serious when {metallic parts,imachines, e. g. aircrafts andrthelike are transported over bodies ofsalt water overdone-periods,ofvtime under humid and .high (tempera u eaQQHdit ions. .Unless the metal surfaces are protected w th pa coatingcomposition which is impervious toaetive corrosion producingagents,serious and damaging corrosion "setsin.

'Such contaminants also have a detrimental effect upon themediurn whichthey are 'diS- persed. In lubricating and liquid fuel mediums 0 theycause oxidation, interfere with the junctign- :-i.at, y compositions.waxes, or anic c m ounds.

e. or c'acids, am nes; norgan c compounds and the like in "order toprotect; them againstcorrosion. "In almost all cases whereno cheniicalreaction occurred between the surface treated and the corrosion .or r, t;inhibitor M6 :little benefit-was derived. i s dueto 'thefact thatnon-chemical reactive'inhibitors are incapableof p n t at n thesl rlfaoebeinaprot oteo anoi in apa e o c pla iug the c ntaminant .theref o Incases where suoh..inhi.bitors.- ar.e.ableto form pr t t v coat n s ,on-.sur a es they ar s y displ ced iby moisture .or rupture vreadily. Theyare relat vel inofiective a a ns or osiv a diomate als-and.n p asesrsuoasare fo med during operation of combustion and urb ue. en-

g os nd are eas y d str yed whenlappliedto surfaces which ,are subjectedto high t,'en 1 tures.

has n w n dis ered that .variousme- 'tail'licsurfaces canbeprotectedagajnst c m i y coating sa d su ces-with arompos onoomprising amajor a unt of .aj1ig-uid.,base.sucl1. as an aromatic s e or aiblend ofaromatic :solv ntand a lia til ouid h drocarhonhavinaa h l nggn nt ntesceedin ,a-roundabout 6.50 F.

said liquidba-se containing a substantial amount Parafiins 'octane,dodecane, cycloparafiins, e. hexane, methylcyclohexane, etc.

solvents may be represented by sulfur dioxide,

phenol, furfural, nitro-benzenacresol, aniline,

beta, beta dichloro-diethyl ether and the like. Hydrocarbons which areparticularly suitable for treatment with above type of solvents arepetroleum hydrocarbons having a boiling range of from about 300 F. toabout 600 F. and may be specifically represented by kerosene, gas oil,light hydrocarbon oil fractions and the like. Particularly preferred arearomatic solvents obtained by the sulfur dioxide treatment of a 300 F.to 370 F. petroleum hydrocarbon out according to the :well knownEdeleanu process. aromatic solvents obtained by subjecting kerosene tothe Edeleanu process are given below.

Characteristics of Aromatic solvents suitable for use as a component ofcompositions of this invention may be obtained by other means thansolvent extraction of petroleum distillates. ,Thus aromatic solvents maybe obtained from catalytic conversion of petroleum hydrocarbons such asobtained ,from recycle stocks from catalytic cracking. Also aromaticssuch as naphthalene, fiuorene, ,phenanthrene anthracene, coal tarresidues and the like, may be admixed in small amounts with aromaticsolvents of the type described above. 7 The aromatic solvents shouldcomprise at least v jabout 45% of the composition.

If desired part of the aromatic solvent may be replaced with a lightliquid hydrocarbon fraction and/or fractions providing the aromaticsolvent constitutes The light liquid hydrocarbon fractions which may beblended with aromatic solvents may be i obtained from any type ofpetroleum base such as parailinic, naphthenic, asphaltic and/or theirfractions.

The fractions desired are those normally liquid fractions which have aboiling point range below that of lubricating oil. Specific liquidhydrocarbons which may be obtained from petroleum distillate by anysuitable means include, kerosene, mineral seal oil, mineral spirits,

light spindle oil, light spray oils, petroleum solvent naphtha as wellas various other petroleum naptha cuts, petroleum ethers, octane, isog.cyclo- To an aromatic solvent or to a blend of an aromatic solvent and ahydrocarbon as described above which generally comprises at least 50%slack waxes, scale waxes, paraflin waxes, plate "Gravity, API, at 60 F35.3-35.2 Spec. gravity, 60/60 F 0.84380.8483 Flash Tag, 00., F 119-112'Aniline pt., F. ASTM 9.0-31 Aromatics, ASTM, percent weight 58-68 Alkylphenols (SMS .246) 11-15 Aromatic free residue, tool 32-42 Naphthenes,mol percent, Maltiello 61-63 37-39 (All line waxes and the like.-entiated from each other by the degree of deoiling to which they aresubjected and all of and/or their mixtures. .methyl, methyl ormethylethyl ether; acetone, diethyl,

of the composition of this invention is added between about 15% to 30%and preferably between about 20 to 30% of a waxy hydrocarbon such asparaffin wax, petrolatum and the like.

The waxy hydrocarbon should be substantially non-aromatic andmay'bederived from petroleum fractions such as petroleum distillates orresidues, or the waxy hydrocarbons may be produced synthetically bypolymerization of olefinic materials such as by the Fischer-Tropschprocess or by dehydration of long chain aliphatic alcohols.

Waxy hydrocarbons may be recovered from suitable petroleum fractionssuch as Pennsylvania crudes, East Texas crudes, Mid-Continent crudes andthe like by de-asphaltizing the hydrocarbon and thereafter removing thewax from the asphalt free hydrocarbon fraction by any known suitablemeans.

In the solvent process a solvent is selected in which the oil'isrelatively soluble but in which the'asphaltic materials are relativelyinsoluble. Among such solvents are the light liquid hydrocarbons such asethane, propane, butane, as well as naphtha and gasoline. The wax-oilmixture :may be removed from the asphalt-free solution by chilling thesolution, and then separating the precipitated wax by settling,filtering, or centrifuging. Waxy materials thus produced are known inthe art as slop waxes, petrolatum stock,

malcrystalline and needle waxes, micro-crystal- The waxes are differthemmay be used provided they are substantially free from aromatics.

De-waxing or separation of the above waxy constituents from the oil maybe accomplished .by selective solvent treatment using as the diluentsliquified normally gaseous hydrocarbons such as propane, butane andother corresponding olefins and/or their mixtures as well asoxygen-containing liquid organic substances such as alcohols, ethers,esters, ketones, aldehydes, acids These may include ethyl, propyl,butyl, amyl alcohols,

dimethyl, methylethyl, methylisobutyl ketones and the like. Chlorinatedhydrocarbons such as carbon tetrachloride or trichloroethylene andmixtures of chlorinated and non-chlorinated hydrocarbons as mentionedabov also may be used.

The firststep in obtaining waxy constituents from petroleum crudes forexample such as Midlower causing separation of the wax from the oil. Thewax can be removed by filtration and the propane separated from thede-asphalted and dewaxed oil and waxy material by distillation.

Waxy materials can also be recovered from distillate or residuum lubeoil fractions and these wax fractions can be split still further intospecial wax cuts having desired character istics by use of selectivesolvents. This is based on a difference in solubility of different waxyfractions in a given solvent.

a methylethyl ketone type solvent the aromatic Thus, when usingsconstituents :can be :removed by successively qxzoolingtthermixture:down-to between: about--40 rand -.7.6 :so as i-to :remove :thearomatics which become substantially soluble-in the-'solvent as thetemperature is lowered While the straight chain waxes .and -isoparaffinsbecome :substantially Iinsoluble .in the solvent. The .straight chainwaxes .can the :separated from :the :isoparafilns by extraction andfractional crystallization. Depending upon the distillate cut usedrwaxes of from 1'2rto aboVe153'6 carbonatoms and higher-scan beobtained.

flinstead o'f o'btaining natural waxy -materialsfrom:petroleumifractions, straight chain waxes can be produced"synthetically (by gpolymefiza- .cluded.013ganic amines and amine saltse. g. .ali-

tion :of olefins :under :pressure of dehydrating tlong chain fatty:alcohols such :as "octadecyl ;al- :cchol :and 'rthe like. Mixtures ofthe :aboveimentioned r'waxes :may 'he :.used in compositions.nfithisinventi'on. .Ifidosired, the waxy hydrocarbon may be oxiidizedby any suitablameans.

The .final :essential ingredient :which :comprises sa -component part:of :compositions of this invention is a lead salt ."ofzan LOrganic.:cyclic :acid; said salt, e. g., lead naphthenate being present in 'anamount'of between about 10 to 25% and pref :erably between about .18to-22% byweight.

-Cyclic acids which maybe used :to form the .;heavy :metal salts .may.be represented by the formula R-(Y)a (Z)b (CXXHM, wherein R is a"cyclicradical; "the Xs 'may be 0, S, 'Se and/or Te; the acid radical(CXXH) being'linked directly or indirectly to'R; Y is a'polar group; Zis an organic radical from the groups consisting-of alkylyalkylene,alkylaryl, aryl alkyl, alkoxy, aroxyl, aryl'radical :and .the like; aandb may bezero -oraninteger of l or 2, and c is an *integer'of -1"or 2."The substituent group represented by Y in "the 'formula may be hydroxy,

amine, nitro, nitroso, halogen, ,sulfo, mercapto,

and the like. The polar group .or groups may .be attached directly orindirectly to theRradical.

Specifically cyclic acidsmay include: naphthenic acid (derived frompetroleum hydrocarbons),,phenyl naphthenic acids, .hydroxy-phenylnaphthenic acids, benzyl naphthenic acids, benzoyl naphthenic acids;naphthyl ,naphthenic :acids, xenyl naphthenic acids, ,phenyl .vinaconicacid, phenyl caronic acid, truxillic acids,,phenyl morphinic acid,phenylepinic.-acid,,phenyl camcarboxylicacidycyzilohexane carboxylicacid, cy-

clohexylacetic acid, cyclohexylbutynic acid, cycloheXyl caproic acid,cylohexylpropionic acid, cyclohexylvaleric .acid, ienchol-ic .acid,!.Ch01l(3 ac'i'd, abietic acid, etc.

The salts of this inventionmaybe obtained..-

by reacting' an organic cyclic acid or mixtures of said-acids with anoxide, "carbonate, sulfide and *the like of lead.

--Some specific salts of organic .cycllc-acids-are listed below in whichthe lead :cation part may .be combined with any of the anion parts.listed toform organic salts of this invention -Anion part .Petroleumnaphthenic acid 26 Phenylnaphtheniczacidv:Hydroxygphenylinaphthenicsacid Naphthyl naphthenic acid vl henylvinaconicwacid 5 Phenyl .binic :acid

Phenyl hexahydrobenzoic acid .Phenyl 'hexahydrophthalicacidTetrahydrotoluic acid Cyclohexadiene carboxylic. acid Cyclohexyl caproicacid inbieticacid If desired, variousadditives may be added :to

compositions "of :this invention to -improve .its properties. Among suchadditives may be inphatic .cycloaliphatic, alkyl amines such asoctadecylamine, cyclohexylamine, dicyclohexylamine, -methy1-cyclohexylamine, .triethanolamine; ,par-

amine oleate, dicyclohexylamine oleate; salts 'of 25 sodium .chromate,etc. ,The amount of theseadditivesis generally .added .in an amountnotexwading-5% and preferably.1,to 3,%,is usual.

-A:.genera1iormula of .a composition .of. this. in vention may consistof the .iollowingcomponents by weight.

:EBroad .Lin'ilted .Ranga :Range 5 Waxyhydrocarbon -35% am.

Lead salt of an organic cyclica'cid ID-25%" I8=22%. Optionaladditivepegg.--amines,'petroleum 075%.... 143%.

:isulfonate. 'Aromaticsolvent and/ormlxture of aromatic balance'balancc.

solvent anda light liquid hydrocarbon.

Specific examples ofa preferred composition (henceforth designated ascomposition A, B, C, *3) of "this invention comprises:

Composition, A

Percent .Lead naphthenate 181-22 .Short residue ,petrolatum 25 .Aromaticsolvent ibalance Composition *8 Per cent mead maphthenate 10320 -Shortresidue petrolatum 20-30 eyclc-hexylamine 11- 3 Aromatic solvent balanceComposition C lHerlcent Lead naphthenate. .l0-15 Oxidizeid..shortresidue-petrolatum 20-.25

.Cyclohexylamine .1-5

Calcium petroleum sulfonate 11-45 Aromatic solvent balance Composition DPercent Lead naphthenate 10-1-20 xidized shcrt'res-idue-petrolatum 20 30Calcium petroleum sulionate '1- '5 Aromatic solvent balance Compositionsof this invention mayrbemrepared by adding at about 180 F.-:vszaxy."hydrocarlzmon such aapetrolatum to a leadbaseiconthe likes-andmixing: the two .atuthis temperature for: about '15 minutes. flhemixture is then slowlyrcool'ednnder agitationito around about F.. rat'-which point the aromatic solvent is slowly added. The mixture is thenreheated to about 120 F. until a homogeneous composition is obtained andcooled to room temperature with continuous agitation.

In order to determine the protective properties compositions of thisinvention possess, various metals were coated with compositions of thisinvention and subjected to the following tests.

Humidity cabinet test coating.

Salt spray test In this test polished steel panels which have beencoated with a desired product to be evaluated are exposed continuouslyat a constant temperature (95 or 100 F.) to a salt mist or fog which isproduced by the atomization of a 20% sodium chloride solution. Theaverage time until rusting occurs on the faces of the panels is taken asthe life of the coating.

Ultraviolet weathering unit test In this test polished or sandblastedsteel panels which have been coated with a desired product to beevaluated are continuously exposed to intense light from a carbon arcand are intermittently wetted by a fine water spray. The average timeuntil rusting occurs on the faces of the panels is taken as the life ofthe coating.

Unsheltered, sheltered, outdoor and indoor exposure test In theunsheltered outdoor exposure test, polished or sandblasted steel panelswhich have been coated with a desired product to be evaluated arefastened on uncovered racks facing south at an angle of 45 degrees fromthe vertical and are exposed continuously until rusting occurs.

The average exposure time of tests conducted during different seasons ofthe year indicates the actual life of the coating. For sheltered outdoorexposure panels are suspended in a cabinet which is open to theatmosphere from the sides or bottom, but the panels are completelyprotected from rain, snow, etc. Indoor exposure test is designed todetermine the protective properties products possess in resistingfluctuation in tem- J perature and relative humidity.

Composition A as noted in column 6 of this invention having thefollowing properties was subjected to the above tests and the resultsare as tabulated below:

Properties of Composition A vGravity at 60 F. API 26.1 Flash, F. (COO)134 Viscosity at 100 F. Saybolt Universal 59 Pour point, F A 40 Testresults -Humidity cabinet, hrs Over 1000 Salt spray, 20%, hrs 280 U-Vweathering unit, hrs Over 300 Unsheltered outdoor exposure, days. Passed120 Sheltered outdoor exposure, mos 12-24 ,Indoor exposure, mos Over 248 The above Composition A was far superior to the best known commercialproduct (X) which when subjected to some of the above desired tests gavethe following results:

Salt spray, 20% hrs 160 Weathering unit, hrs Unsheltered outdoorexposure, days Failed 14 Compositions of this invention may if desired,be very easily removed by flushing, wiping or any other suitable means.Compositions of this invention may also be applied to non-metallicsurfaces which require protection against corrosion, moisture, theelements and the like.

Many modifications and variations of this invention as hereinbefore setforth may be made without departing from the spirit and. scope thereofand therefore only such limitation should be imposed as indicated in theappended claims.

We claim as our invention:

1. A rust inhibiting composition of matter consisting essentially of thefollowing constituents in the following proportions:

Per cent by weight Lead naphthenate 15-25 Short residue petrolatum 25-30Aromatic solvent Balance 2. A rust inhibiting composition of matterconsisting essentially of the following constituents in the followingproportions:

Per cent by Weight Lead naphthenate 15-25 Short residue petrolatum 20-30Cyclohexylamine 1- 5 Aromatic solvent Balance 3. A rust inhibitingcomposition of matter consisting essentially of from about 15 to 35% ofa petroleum wax, from about 10 to 25% of lead salt of naphthenic acidand the balance being an aromatic solvent.

4. A rust inhibiting composition of matter consisting essentially of amajor proportion of an aromatic solvent, a minor amount of about 30% ofa petroleum wax, and about 20% of lead salt of naphthenic acid.

5. A rust-inhibiting composition of matter consisting essentially of thefollowing constituents in the following proportions:

Per cent by weight Lead naphthenate 18-22 Short residue petrolatum 25-30Aromatic solvent Balance KNAPEL F. SCI-IIERMEIER. HERBERT A. POITZ.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,060,138 Taylor Nov. 10, 1936 2,124,446 Detwiler July 19,1938 2,182,992 Lebo Dec. 12, 1939 2,184,952 Zimmer et al Dec. 26, 19392,334,071 Cook et a1 Nov. 9, 1943 2,348,715 Adams et al May 16, 19442,359,946 Sudholz et al. Oct. 10, 1944 2,415,353 Johnston et a1 Feb. 4,1947

3. A RUST INHIBITING COMPOSITION OF MATTER CONSISTING ESSENTIALLY OFFROM ABOUT 15 TO 35% OF A PETROLEUM WAX, FROM ABOUT 10 TO 25% OF LEADSALT OF NAPHTHENIC ACID AND THE BALANCE BEING AN AROMATIC SOLVENT.